自然界中同一元素往往含有不同的物種型態，而物種間的毒性及特性也有所不同，相較於總量的測定，物種分析的結果更能夠完整的提供樣品資訊。利用高效能液相層析 (High Performance Liquid Chromatography，HPLC)將物種分離後，搭配感應耦合電漿質譜儀 (Inductively Coupled Plasma Mass Spectrometry，ICP-MS)偵測，其具有高重複性、低偵測極限、線性範圍廣及同位素分析能力等優點，成為物種分析工具最佳選擇之一；在分析真實樣品中往往會有不同於物種標準品的未知物種，利用電噴灑質譜儀 (Electrospray Ionization Mass Spectrometry，ESI-MS)針對未知物種進行鑑定，可以得到定量以及定性完整的資訊。
第一部分研究，使用陰離子交換樹脂 (Anion-exchange chromatography)作為管柱，以碳酸銨作為動相分離人體尿液中含砷與硒化合物，本實驗系統可以於11分鐘內分離AsB、As(III)、DMA、MMA、As(V)、Se(IV)及Se(VI)等七種砷與硒物種。分析時使用動態反應槽 (Dynamic Reaction Cell)以去除高鹽類樣品中的氯離子形成ArCl對於砷的光譜干擾，以及去除ICP系統中Ar氣體形成Ar2對於硒的光譜干擾。在最適化條件下，砷的偵測極限範圍介於0.008-0.015 ng mL-1；硒的偵測極限範圍介於0.022-0.030 ng mL-1。將此方法應用在分析NIST 2670以及來自三種不同的尿液樣品中。在分析結果中發現尿液樣品含有硒物種的未知物。將液相層析連接電噴灑質譜儀系統 (HPLC-ESI-MS)鑑定未知物，經過一次質譜和二次質譜的鑑定後，可能為硒醣 (SeSug1)。由於人與人之間飲食習慣不同，而使得尿液中砷與硒總量及物種上有所差異，經過服用含硒的補給品，可以幫助人體代謝，使得尿液中砷含量提高。
第二部分研究，以陰離子交換層析結合感應耦合電漿質譜儀對營養補給品中Cr(III)、Cr(VI)、AsB、As(III)、DMA、MMA及As(V)等物種進行分析。動相中添加EDTA作為與Cr(III)的螯合試劑，幫助鉻的分離。以梯度沖提方式在層析最適化條件下於14分鐘內分離七種物種。為了減輕鉻在偵測時來自ArC的光譜干擾，選用O2作為DRC系統的反應氣體。在最適化條件下，砷的偵測極限範圍介於0.008-0.019 ng mL-1；鉻的偵測極限範圍介於0.084-0.087 ng mL-1。方法確效上選用NRCC DORM-3，樣品則為藥局販售之營養補給品。樣品萃取方法採用微波輔助萃取，萃取試劑為2 mM EDTA及1% HF配製於含有50 mM 碳酸銨的動相B中，與微波消化結果比較後，萃取效率介於88-95%之間。在萃取前添加標準品，確認此萃取方法不會造成物種間的轉換，其回收率介於91-103%之間，證實此萃取方法的可行性。根據實驗結果顯示，自然界食品中的鉻以Cr(III)為主，由於食品中含有抗氧化劑，大部分的Cr(III)不會被氧化成Cr(VI)。

First research, speciation of arsenic and selenium in human urine was carried out using ion chromatography (IC) for separation and inductively coupled mass spectrometry (ICP-MS) for detection. The arsenic and selenium species studied were arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and selenite [Se(IV)], selenate [Se(IV)]. Chromatographic separation of all the species was achieved in <11 min in gradient elution mode using (NH4)2CO3 and methanol at pH 8.8. The outlet of the IC column was directly connected to the nebulizer of ICP-MS for the determination of arsenic and selenium. The speciation of arsenic and selenium have been carried out in human urine samples. The recoveries from spiked samples were in the range of 91−109%. The unknown compounds detected in human urine were identified by coupling IC directly with electrospray ionization−mass spectrometry (ESI-MS). Selenosugar was identified in human urine. The limits of detection were in the range of 0.008−0.015 ng mL−1 for various arsenic species and 0.022-0.030 ng mL−1 for various selenium species based on peak height.
Second research, a HPLC separation procedure has been developed for the speciation of Cr(III), Cr(VI) and As(III), As(V), DMA, MMA, AsB in dietary supplement samples. The species were separated on anion-exchange LC in gradient elution mode. The mobile phase consisting of EDTA and (NH4)2CO3 at pH 8.8, operated in a linear ramp, yielded well resolved chromatograms of all the species within 14 min with retention times of less than 2% RSD. The analyses were carried out using dynamic reaction cellinductively coupled plasma-mass spectrometer (DRC-ICP-MS). The DRC conditions have also been optimized to obtained interference free measurements of 52Cr, 53Cr and 75As, which were otherwise interfered by: 35Cl16O1H, 40Ar12C on 52Cr; 37Cl16O, 40Ar13C, 40Ar12C1H on 53Cr; and 40Ar35Cl on 75As. The detection limits of the procedure were 0.008-0.019 ng As mL-1 and 0.084-0.087 ng Cr mL-1. The accuracy of the method has been validated by comparing the sum of the concentrations obtained for individual species with total concentration of the elements in NRCC SRM DORM-3 Fish Protein. The method has also been applied on three real samples, diabetic support formula tablets, diabetic support formula dietary fiber and Spirulina tablets , in which case the comparison has been made with total concentrations determined after complete dissolution of the samples. In this study, a microwave-assisted extraction method was used for the extraction of chromium and arsenic species from dietary supplemen samples. The extraction efficiency was better than 88% and the recoveries from spiked samples were in the range of 91–103%.

目錄
謝誌 ................................................................................................................................... i
摘要 .................................................................................................................................. ii
目錄 ................................................................................................................................... v
圖目錄 ............................................................................................................................ vii
表目錄 ............................................................................................................................. ix
第一章 液相層析結合感應耦合電漿質譜儀與電噴灑質譜儀於尿液樣品中砷與硒物種分析之應用
壹、前言 ........................................................................................................................... 1
貳、動態反應槽 (Dynamic Reaction Cell，DRC)原理 ................................................. 6
參、實驗部分
一、儀器裝置 ........................................................................................................... 7
二、藥品與溶液之配製 ......................................................................................... 10
肆、實驗流程
一、液相層析條件最適化 ..................................................................................... 15
二、DRC-ICP-MS系統最適化探討 ..................................................................... 15
三、再現性 ............................................................................................................. 17
四、校正曲線與偵測極限的估計 ......................................................................... 17
五、真實樣品分析 ................................................................................................. 17
伍、結果與討論
一、液相層析最適化探討 ..................................................................................... 18
二、DRC-ICP-MS系統最適化探討 ..................................................................... 21
三、再現性 ............................................................................................................. 34
四、校正曲線與偵測極限的估計 ......................................................................... 34
五、真實樣品分析 ................................................................................................. 40
陸、結論 ......................................................................................................................... 55
柒、參考文獻 ................................................................................................................. 56
第二章 液相層析結合感應耦合電漿質譜儀與電噴灑質譜儀於營養補給品中鉻與砷物種分析之應用
壹、前言 ......................................................................................................................... 60
貳、實驗部分
一、儀器裝置 ......................................................................................................... 64
二、藥品與溶液之配製 ......................................................................................... 64
參、實驗流程
一、液相層析條件最適化 ..................................................................................... 66
二、DRC-ICP-MS系統最適化探討 ..................................................................... 67
三、再現性 ............................................................................................................. 69
四、校正曲線與偵測極限的估計 ......................................................................... 69
五、真實樣品分析 ................................................................................................. 69
肆、結果與討論
一、液相層析最適化探討 ..................................................................................... 70
二、DRC-ICP-MS系統最適化探討 ..................................................................... 81
三、再現性 ............................................................................................................. 92
四、校正曲線與偵測極限的估計 ......................................................................... 92
五、萃取最適化條件 ............................................................................................. 98
六、真實樣品分析 ............................................................................................... 102
伍、結論 ....................................................................................................................... 112
陸、參考文獻 ............................................................................................................... 113
圖目錄
第一章 液相層析結合感應耦合電漿質譜儀與電噴灑質譜儀於尿液樣品中砷與硒物種分析之應用
圖1-1 HPLC-DRC-ICP-MS系統圖 ............................................................................ 9
圖1-2 砷與硒物種之結構式 ..................................................................................... 12
圖1-3 砷與硒物種於各pH值環境下之化學式及pKa值 ...................................... 14
圖1-4 動相A與B的pH值對層析結果的影響 ..................................................... 19
圖1-5 動相B中碳酸銨濃度對層析結果的影響 .................................................... 20
圖1-6 動相中MeOH濃度對層析結果的影響 ........................................................ 22
圖1-7 注入5 ng mL-1砷標準品與200 μg mL-1氯離子之層析圖 .......................... 25
圖1-8 以O2為反應氣體，設定q值為0.7，改變氣體流速對(a) 75As；(b) 75As16O及背景訊號的影響 ........................................................................................ 27
圖1-9 以O2為反應氣體，設定q值為0.7，改變氣體流速對(a) 78Se；(b) 80Se；(c) 78Se16O；(d) 80Se16O及背景訊號的影響 ...................................................... 28
圖1-10 以CH4為反應氣體，設定q值為 0.7，改變氣體流速對(a) 75As；(b) 75As12CH2；(c) 75As12CH3；(d) 75As12CH4及背景訊號的影響 ................... 29
圖1-11 以CH4為反應氣體，設定q值為 0.7，改變氣體流速對(a) 78Se；(b) 80Se及背景訊號的影響 ........................................................................................ 30
圖1-12 以O2為反應氣體，設定q值為0.7，改變氣體流速所得訊號強度與背景訊號之比值 (S / B)以及預估偵測極限 (EDL) ......................................... 31
圖1-13 以CH4為反應氣體，設定q值為0.7，改變氣體流速所得訊號強度與背景訊號之比值 (S / B)以及預估偵測極限 (EDL).......................................... 32
圖1-14 以O2為反應氣體，設定氣體流速為1.4 mL min-1，改變Rpq值對預估偵測極限 (EDL)的影響..................................................................................... 33
圖1-15 以O2為反應氣體，設定氣體流速為1.4 mL min-1，Rpq值為0.5 (AsO)、0.6 (Se)，改變AFV對砷及硒分析物和背景訊號之影響 .......................... 35
圖1-16 不同模式下砷與硒物種之層析圖 ................................................................. 37
圖1-17 人體尿液稀釋倍數對層析結果的影響 ......................................................... 44
圖1-18 人體尿液注入HPLC-ESI-MS所得圖譜 ........................................................ 46
圖1-19 標準參考樣品2670 “Normal Level” Freeze-dried Urine稀釋5倍之層析圖......................................................................................................................... 47
圖1-20 標準參考樣品2670 “Elevated Level” Freeze-dried Urine稀釋10倍之層析圖 ..................................................................................................................... 49
圖1-21 人體尿液#1稀釋5倍之層析圖 .................................................................... 51
圖1-22 人體尿液#2稀釋5倍之層析圖 .................................................................... 52
圖1-23 人體尿液#3稀釋5倍之層析圖 .................................................................... 53
第二章 液相層析結合感應耦合電漿質譜儀與電噴灑質譜儀於營養補給品中鉻與砷物種分析之應用
圖2-1 三種常見的螯合試劑 ..................................................................................... 63
圖2-2 實驗流程圖 ..................................................................................................... 71
圖2-3 樣品萃取流程圖 ............................................................................................. 73
圖2-4 動相A與B的pH值對層析結果的影響 ..................................................... 75
圖2-5 動相B中碳酸銨濃度對層析結果的影響 .................................................... 76
圖2-6 動相A與B中EDTA的濃度對層析結果的影響 ....................................... 78
圖2-7 動相中添加MeOH濃度對層析結果的影響 ................................................ 79
圖2-8 動相流速對層析結果的影響 ......................................................................... 80
圖2-9 注入10 ng mL-1砷標準品與200 μg mL-1氯離子之層析圖 ........................ 83
圖2-10 以O2為反應氣體，設定q值為 0.7，改變氣體流速對(a) 52Cr；(b) 53Cr；(c) 75As； (d) 75As16O及背景訊號的影響 ................................................... 84
圖2-11 以CH4為反應氣體，設定q值為 0.7，改變氣體流速對(a) 52Cr； (b) 53Cr 及背景訊號的影響 ............................................................................................. 85
圖2-12 以CH4為反應氣體，設定q值為 0.7，改變氣體流速對(a) 75As；(b) 75As12CH2； (c) 75As12CH3；(d) 75As12CH4 及背景訊號的影響 ................. 86
圖2-13 以O2為反應氣體，設定q值為 0.7，改變氣體流速所得訊號強度與背景訊號之比值 (S / B)以及預估偵測極限 (EDL) ......................................... 88
圖2-14 以CH4為反應氣體，設定q值為 0.7，改變氣體流速所得訊號強度與背景訊號之比值 (S / B)以及預估偵測極限(EDL).............................................. 89
圖2-15 以 CH4為反應氣體，設定氣體流速為 1.0 mL min-1，改變Rpq值對預估偵測極限 (EDL)的影響 ................................................................................. 90
圖2-16 以 O2為反應氣體，設定氣體流速為 0.8 mL min-1，改變Rpq值對預估偵測極限 (EDL)的影響..................................................................................... 91
圖2-17 以 O2為反應氣體，設定氣體流速為 0.8 mL min-1，Rpq值為 0.60，改變AFV對鉻及砷分析物和背景訊號之影響.................................................... 93
圖2-18 鉻與砷物種在不同模式下之層析圖 ............................................................. 95
圖2-19 添加不同濃度EDTA於萃取液中，探討糖尿病補給錠中鉻之相對訊號 ....................................................................................................................... 100
圖2-20 添加不同的酸試劑於萃取液中，探討糖尿病補給錠中鉻之相對訊號 ... 101
圖2-21 標準參考樣品DORM-3 Fish protein萃取後所得鉻與砷之層析圖 .......... 104
圖2-22 糖尿病配方補給錠萃取後所得鉻與砷之層析圖 ....................................... 106
圖2-23 糖尿病補給纖食萃取後所得鉻與砷之層析圖 ........................................... 108
圖2-24 市售綠藻錠萃取後所得鉻與砷之層析圖 ................................................... 110
表目錄
第一章 液相層析結合感應耦合電漿質譜儀與電噴灑質譜儀於尿液樣品中砷與硒物種分析之應用
表1-1 各物種化合物之半數致死量 ........................................................................... 2
表1-2 尿液中砷與硒物種的文獻回顧 ....................................................................... 5
表1-3 砷與硒物種之化學式與解離常數pKa值 ..................................................... 13
表1-4 以ICP-MS分析砷與硒時常見之光譜干擾 .................................................. 16
表1-5 動相中甲醇濃度對於分析物訊號之影響 ..................................................... 23
表1-6 液相層析系統之最適化分離條件 ................................................................. 24
表1-7 HPLC-DRC-ICP-MS系統操作條件 .............................................................. 36
表1-8 以LC-DRC-ICP-MS測定5 ng mL-1砷物種及20 ng mL-1硒物種之滯留時間與分析物訊號再現性................................................................................. 38
表1-9 以HPLC- ICP-MS測定砷及硒物種之校正曲線及偵測極限 ..................... 39
表1-10 砷與硒物種偵測極限之比較 ......................................................................... 43
表1-11 HPLC-ESI-ITMS系統操作參數 .................................................................... 45
表1-12 以LC-DRC-ICP-MS測定NIST 2670 NIST 2670 “Normal Level”標準參考樣品中之砷及硒物種 ..................................................................................... 48
表1-13 以LC-DRC-ICP-MS測定NIST 2670 “Elevated Level”標準參考樣品中之砷及硒物種 ......................................................................................................... 50
表1-14 以LC-DRC-ICP-MS測定人體尿液中之砷及硒物種 .................................. 54
第二章 液相層析結合感應耦合電漿質譜儀與電噴灑質譜儀於營養補給品中鉻與砷物種分析之應用
表2-1 以ICP-MS分析鉻與砷時常見之光譜干擾 ..................................................... 68
表2-2 微波消化步驟設定參數 ................................................................................. 72
表2-3 液相層析系統之最適化分離條件 ................................................................. 82
表2-4 HPLC-DRC-ICP-MS系統操作條件 .............................................................. 94
表2-5 以LC-DRC-ICP-MS測定10 ng mL-1鉻及5 ng mL-1砷物種之滯留時間與分析物訊號再現性 ......................................................................................... 96
表2-6 以HPLC- ICPMS測定鉻及砷物種之校正曲線及偵測極限 ....................... 97
表2-7 鉻與砷物種偵測極限之比較 ......................................................................... 99
表2-8 以LC-DRC-ICP-MS測定NIST DORM-3標準參考樣品中之鉻及砷物種 ....................................................................................................................... 105
表2-9 以LC-DRC-ICP-MS測定糖尿病補給錠中之鉻及砷物種 ........................ 107
表2-10 以LC-DRC-ICP-MS測定市售糖尿病配方纖食中之鉻及砷物種 ............ 109
表2-11 以LC-DRC-ICP-MS測定市售綠藻錠中之鉻及砷物種 ............................ 111

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